EP4286040A1 - Double émulsion et capsules - Google Patents

Double émulsion et capsules Download PDF

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Publication number
EP4286040A1
EP4286040A1 EP22305808.2A EP22305808A EP4286040A1 EP 4286040 A1 EP4286040 A1 EP 4286040A1 EP 22305808 A EP22305808 A EP 22305808A EP 4286040 A1 EP4286040 A1 EP 4286040A1
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EP
European Patent Office
Prior art keywords
oil
phase
aqueous phase
water
oil phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22305808.2A
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German (de)
English (en)
Inventor
Claire NANNETTE
Jean Baudry
Jerome Bibette
Damien DEMOULIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Calyxia SAS
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Calyxia SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Calyxia SAS filed Critical Calyxia SAS
Priority to EP22305808.2A priority Critical patent/EP4286040A1/fr
Priority to PCT/EP2023/064800 priority patent/WO2023232993A1/fr
Publication of EP4286040A1 publication Critical patent/EP4286040A1/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95

Definitions

  • the present invention relates to a water-in-oil-in-water double emulsion, a method for the manufacture of a water-in-oil-in-water double emulsion, solid microcapsules and a method for the manufacture of solid microcapsules.
  • Encapsulating and isolating active agents allows the protection thereof from the surrounding environment and in particular from hydrolysis, thermal degradation, oxidation, cross-reactivity or other processes that may reduce their performance.
  • the present invention aims at providing a method for manufacturing solid microcapsules without using surfactants during the elaboration of emulsions.
  • the encapsulation yield is particularly low, based on techniques disclosed in the prior art, for hydrophilic active agents.
  • the continuous phase is generally aqueous and the hydrophilic active tends to disperse in the continuous phase rather than being encapsulated by the oligomeric phase, due to osmotic pressure between the innermost aqueous phase and the external aqueous phase, through the oil middle phase.
  • the present invention aims at providing a method in one step for manufacturing a double emulsion without surfactants and an encapsulation method optimally suited for hydrophilic active agents.
  • the present inventors have surprisingly discovered a method for manufacturing water-in-oil-in-water double emulsions that have the particular advantage of being able to formulate remarkably stable invert emulsions, said method being in one-step, without the use of a surfactant, allowing the encapsulation of more hydrophilic active agent than the prior art methods (which generally allows the encapsulation of about 5-20% w/w of active agent relative to the total weight of the emulsion). Indeed, phases separation in the emulsion occurs only several hours after the emulsion is formed and left at rest.
  • the present invention relates to a method for the manufacture of a water-in-oil-in-water double emulsion, comprising:
  • the addition dropwise of the aqueous phase to the oil phase occurs at a rate ranging from 0.001 mL.s -1 to 50 mL.s -1 , preferably from 0.001 mL.s -1 to 20 mL.s -1 , more preferably from 0.001 mL.s -1 to 10 mL.s -1 , even more preferably from 0.001 mL.s -1 to 0.2 mL.s -1 , better from 0.001 mL.s -1 to 0.05 mL.s -1 , still better of about 0.01 mL.s -1 .
  • the mixture comprising the aqueous phase and the oil phase is continuously stirred, preferably at a stirring speed ranging from 100 rpm to 3000 rpm, more preferably at a stirring speed ranging from 500 rpm to 2500 rpm. More advantageously, the shear rate applied during stirring ranges from 1000 s -1 to 4000 s -1 , preferably from 2000 s -1 to 3000 s -1 .
  • said double emulsion does not comprise surfactant.
  • the ratio between the dynamic viscosity of the innermost aqueous phase and the viscosity of the oil phase ranges from 0.01 to 20, preferably from 0.01 to 10, more preferably from 0.1 to 10, even more preferably from 1 to 10.
  • the dynamic viscosities may in particular be measured using a TA Instruments AR-G2 rheometer equipped with a 3 cm diameter, 2-degree angle cone and a temperature control cell set at 25°C.
  • the interfacial tension ⁇ between the aqueous phase and the oil phase ranges from 0 J.m -2 to 50 ⁇ 10 -3 J.m -2 , preferably from 20 ⁇ 10 -3 J.m -2 to 40 ⁇ 10 -3 J.m -2 .
  • the oil phase comprises at least one compound selected from oligomers, monomers and mixtures thereof, and optionally at least one photo initiator.
  • the present invention also relates to a water-in-oil-in-water double emulsion obtained by the method according to the invention for the manufacture of a water-in-oil-in-water double emulsion.
  • the present invention also relates to a water-in-oil-in-water double emulsion, comprising two aqueous phases (an innermost and an external aqueous phases) and one oil phase, wherein one of the two aqueous phases (the innermost aqueous phase) is entrapped in the oil phase and the second aqueous phase (the external aqueous phase) entraps the oil phase, wherein the two aqueous phases comprise the same composition, wherein the adhesion energy between two droplets of the innermost aqueous phase dispersed in the oil phase ranges from 10 -5 J.m -2 to 10 -3 J.m -2 .
  • said double emulsion does not comprise surfactant.
  • the ratio between the dynamic viscosity of the innermost aqueous phase and the viscosity of the oil phase ranges from 0.01 to 20, preferably from 0.01 to 10, more preferably from 0.1 to 10, even more preferably from 1 to 10.
  • the dynamic viscosities may in particular be measured using a TA Instruments AR-G2 rheometer equipped with a 3 cm diameter, 2-degree angle cone and a temperature control cell set at 25°C.
  • the interfacial tension ⁇ between the innermost aqueous phase and the oil phase ranges from 0 J.m -2 to 50 ⁇ 10 -3 J.m -2 , preferably from 20 ⁇ 10 -3 J.m -2 to 40 ⁇ 10 -3 J.m -2 .
  • the oil phase comprises at least one compound selected from oligomers, monomers and mixtures thereof, and optionally at least one photo initiator.
  • the present invention also relates to a method for preparing solid microcapsules comprising the steps of:
  • the step b) of crosslinking is carried out by submitting the double emulsion to a source of light, preferably a source of UV light.
  • the present invention also relates to a solid microcapsule obtained by the method according to the invention for preparing solid microcapsules.
  • the present invention further relates to a solid microcapsule comprising:
  • the aqueous phase comprises at least one hydrophile active agent.
  • said solid microcapsule comprises greater than or equal to 20% by weight, more preferably from 20% to 80% by weight, even more preferably from 40% to 60% by weight, better about 50% by weight, of at least one hydrophile active agent, the weight percentages being expressed relative to the total weight of said solid microcapsule.
  • the ratio of the weight of the entrapped aqueous phase to the weight of the polymer network ranges from 20 to 70.
  • Active agent refers to a substance that has an effect, in particular in a field selected from the group consisting of therapeutic, cosmetic, agriculture, home care, chemical, paint, fuel, lubricant, bitumen, and drilling sludges or muds.
  • the agent may be a chemical or a biological substance.
  • the active agent is a chemical substance.
  • the active agent is selected from the group consisting of:
  • Additional monomers or oligomers refers to monomers or oligomers bearing at least one pH sensitive group, temperature sensitive group, ultraviolet (UV) sensitive group and/or infrared (IR) sensitive group. These additional monomers or oligomers can induce the rupture of the solid microcapsules according to the invention and subsequently the release of their contents, after stimulation via change in pH or temperature, or exposure to UV or IR radiation.
  • these additional monomers or oligomers may be selected from the group consisting of those:
  • Adhesion refers to the ability of suspended particles or droplets to stick together when approaching closely. When two droplets come into close contact, their surface can deform resulting in the occurrence of a contact angle ⁇ between them. Adhesion can thus be also described as "wetting”. Adhesion takes place into systems where there exists an attractive interaction between both O/W interfaces. This interaction can be attributed to intermolecular forces, chain entanglements, or both, across the interfaces. Adhesion in a system of aqueous droplets suspended in an external oil phase can be quantitatively characterized through the measurement of an "adhesion energy". The adhesion energy may be measured by any method known by the person skilled in the art.
  • Adhesion test with a micropipette aspiration refers to one exemplary method of determining the adhesion between two drops, the method comprising the use of a micropipette aspiration for adhesion testing as represented in Figure 7 , allowing the precise determination of the oil film size using a confocal microscope.
  • Aqueous phase refers to a solution comprising a solvent and optionally at least one solute, wherein said solvent is selected from the group consisting of water, hydrophilic organic solvents and combinations thereof.
  • the aqueous phase and the oil phase are immiscible in each other, which means that the amount by weight of the aqueous phase capable of being solubilized in the oil phase is less than or equal to 5%, preferably less than 1%, more preferably less than 0, 5%, even preferably of 0%, based on the total weight of the oil phase, and that the amount (by weight) of the oil phase capable of being solubilized in the aqueous phase is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, even preferably of 0%, based on the total weight of the aqueous phase.
  • the immiscibility between the aqueous phase and the oil phase makes it possible to avoid migration of active agent(s) optionally present in the aqueous
  • Catastrophic inversion or “phase inversion” or “continuity inversion” refers to a change in the mutual dispersion of two phases in contact in an emulsion.
  • the catastrophic inversion may allow the change of a W/O simple emulsion to a O/W simple emulsion or to a W/O/W double emulsion.
  • the catastrophic inversion allows the change of a W/O emulsion to a W/O/W emulsion.
  • “Comprising” or “comprise” is to be construed in an open, inclusive sense, but not limited to. In an embodiment, “comprising” means “consisting essentially of”. In an embodiment, “comprising” means “consisting of', which is to be construed as limited to.
  • Crosslinkable refers to a composition capable of polymerizing (crosslinking) to give a solid material, to form the polymerized shell and network of solid microcapsules according to the invention.
  • Crosslinking agent refers to a compound carrying at least two reactive functions capable of crosslinking a monomer or an oligomer, or a mixture of monomers or oligomers, during its polymerization.
  • the crosslinking agent may be selected from molecules carrying at least two functions selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate and peroxide functions.
  • the crosslinking agent may be selected from the group consisting of:
  • Drop refers to a small liquid particle.
  • Single drop refers to a drop consisting of a single drop phase.
  • Double drop refers to a drop comprising two phases in the drop, organized in the form of at least one internal drop (composed of one phase) surrounded by an external drop (composed of the other phase).
  • Embodision refers to a fluid colloidal system in which liquid droplets are dispersed in a liquid. The droplets often exceed the usual limits for colloids in size.
  • W/O/W also named water-in-oil-in-water double emulsion, i.e.
  • aqueous droplets contained within oil droplets dispersed in a continuous aqueous phase).
  • the internal emulsion refers to the emulsion of the innermost aqueous phase W(1) in the oil phase O; and the external emulsion refers to the emulsion of the oil phase O in the external aqueous phase W(2).
  • From X to Y refers to the range of values between X and Y, the limits X and Y being included in said range.
  • Hydrophilic or “hydrophile” refers to the capacity of a molecular entity to interact with polar solvents, in particular with water.
  • inclusions refers to spaces in a polymer (the host), in which molecular entities of a second chemical species (the guest) are located.
  • said spaces may be in the shape of long tunnels, channels, or hollow (in particular hollow shaped like a ball or like a drop).
  • the spaces in the polymer lattice are enclosed on all sides so that the guest species is 'entrapped' as in a cage.
  • the guest is the aqueous phase according to the invention.
  • the polymer host is a polymer issued from the polymerization of the oil phase according to the invention.
  • Photoinitiator refers to any substance introduced in the oil phase in order to bring about a polymerization reaction when said initiator is excited by a source of energy.
  • Photoinitiator refers to any substance introduced in the oil phase in order to bring about a polymerization reaction when said initiator is excited by a light radiation.
  • the photoinitiators may be selected from the group consisting of:
  • Inverting emulsion or “inverse emulsion” refers to an emulsion in which the mutual dispersion of two phases in contact with each other has changed.
  • Mean diameter refers to the Dn 50 diameter.
  • Dn 50 is the median of the number averaged size distribution of the droplets or (micro)capsules.
  • the size distribution of the droplets or (micro)capsules, and thus the mean diameter of the droplets or (micro)capsules may be measured by methods well known to the skilled person in the art, e.g. by a light scattering technique (for example using a Mastersizer 3000 equipped with a hydro SV measuring cell), or by image analysis of optical microscopy pictures, or by image analysis of electronic microscopy pictures (TEM - Transmission electron microscopy).
  • “Monomer” refers to a molecule which can undergo polymerization thereby contributing constitutional units to the essential structure of a macromolecule.
  • “Oligomer” refers to a macromolecule comprising a repetition of monomers, preferably a repetition of less than 10 monomers.
  • the "monomers or oligomers” may be selected from monomers and oligomers comprising at least one reactive function selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate and peroxide functions.
  • the monomers or oligomers may be selected from the group consisting of aliphatic or aromatic esters or polyesters, urethanes or polyurethanes, anhydrides or polyanhydrides, saccharides or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates or polycarbonates, wherein the monomers or oligomers further include at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate, and carboxylate moieties.
  • the monomers or oligomers may be selected from monomers or oligomers bearing at least one of the above-mentioned reactive functions and additionally bearing at least one function selected from the group consisting of primary, secondary and tertiary alkylamine functions, quaternary amine functions, sulfate, sulfonate, phosphate, phosphonate, carboxylate, hydroxyl, halogen functions and mixtures thereof.
  • Oil phase refers to a phase not miscible with an aqueous phase, which means that the amount by weight of an aqueous phase capable of being solubilized in the oil phase is less than or equal to 5%, preferably less than 1%, more preferably less than 0, 5%, even preferably of 0%, based on the total weight of the oil phase, and that the amount (by weight) of the oil phase capable of being solubilized in an aqueous phase is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, even preferably of 0%, based on the total weight of the aqueous phase.
  • the oil phase does not necessarily contain oil.
  • the phase oil has typically a viscosity greater than the water viscosity.
  • the oil phase comprises oligomers, monomers and optionally initiators (such as photoinitiators). More advantageously, the oil phase may further include at least one oil. Even more advantageously, the phase oil may further comprise at least one oil selected from the group consisting of silicone oils, mineral oils and mixtures thereof.
  • the silicone oils may be selected from the group consisting of poly(dimethylsiloxane) (PDMS), poly(monomethylsiloxane) (PPMS), poly(dimethylsiloxane) hydroxy terminated (PDMS-OH) and mixtures thereof.
  • the mineral oils may be selected from the group consisting of soybean oil, sunflower oil, jojoba oil, coconut oil, lanolin oil, castor oil, derivatives thereof and mixtures thereof.
  • Polymer refers to a substance composed of macromolecules, said macromolecules comprising multiple repetition of monomers.
  • the polymers may be selected from the group consisting of polyethers, polyepoxides, polyesters, polyurethanes, polyureas, polyethylene glycols, polypropylene glycols, polyamides, polyacetals, polyimides, polyolefins, polysulfides and polydimethylsiloxanes. More advantageously, the polymer may be selected from the group consisting of polyesters, polyepoxides, and polyurethanes.
  • said polymers further carry at least one reactive functionality selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate, and peroxide functionality.
  • the polymers may be selected from the group consisting of: poly(2-(1-naphthyloxy)-ethyl acrylate), poly(2-(2-naphthyloxy)-ethyl acrylate), poly(2-(2-naphthyloxy)-ethyl methacrylate), polysorbitol dimethacrylate, polyacrylamide, poly((2-(1-naphthyloxy) ethanol), poly(2-(2-naphthyloxy) ethanol), poly(1-chloro-2,3-epoxypropane), poly(n-butyl isocyanate), poly(N- vinyl carbazole), poly(N-vinyl pyrrolidone), poly(p-benzamide), poly(p-chlorostyrene), poly(p-methyl styrene), poly(p-phenylene oxide), poly(p-phenylene sulfide), poly(N-(methacryloxyethyl
  • the polymer may have a molecular weight greater than 5000 g.mol -1 , preferably from 10,000 g.mol -1 to 500,000 g.mol -1 , more preferably from 50,000 g.mol -1 to 300,000 g.mol -1 .
  • Branched polymer refers to a polymer having at least one branching point between its two end groups, a branching point being a point of a chain to which is attached a side chain also called branch or hanging chain.
  • a branched polymer may in particular be selected from the group consisting of grafted, comb or star polymers and dendrimers.
  • Polymerization refers to the process of converting a monomer mixture of monomers into a polymer.
  • Rpm or “revolutions per minute” refers to the number of turns in one minute.
  • Shear rate Y refers to the velocity gradient in a flowing fluid.
  • the "shear stress ⁇ " applied to an emulsion drop is defined as the tangential force per unit drop area resulting from the macroscopic shear applied to the emulsion during its agitation.
  • “Surface tension ⁇ ” refers to the work required to increase a surface area divided by that area. When two phases are studied it is called “interfacial tension ⁇ "; “interfacial tension ⁇ ” is the change in Gibbs energy per unit change in interfacial area for substances in physical contact.
  • “Surfactant” refers to a substance which lowers the surface tension of the medium in which it is dissolved, and/or the interfacial tension with other phases, and, accordingly, is positively adsorbed at the liquid/vapour, liquid/liquid and/or at other interfaces.
  • Viscosity or “dynamic viscosity” refers, for a laminar flow of a fluid, to the ratio of the shear stress to the velocity gradient perpendicular to the plane of shear. Viscosity may be measured by methods well-known to a skilled person in the art. Unless otherwise indicated, viscosity, in the present application, is measured by any viscosity measurement method well known to person skilled in the art.
  • viscosity may be measured using a TA Instruments AR-G2 rheometer equipped with a 3 cm diameter, 2-degree angle cone with a plate geometry and a temperature control cell set at 25°C, the viscosity value being read at a shear rate ranging from 0.1 s -1 to 1000 s -1 , preferably at a shear rate equal to 10 s -1 .
  • ⁇ is the w/w percentage of the dispersed phase incorporated into the simple emulsion, relative to the total weight of the simple emulsion.
  • ⁇ int is the w/w percentage of the innermost dispersed phase incorporated into the middle phase, relative to the total weight of said double emulsion; for example, in a water(1)-in-oil-in-water(2) double emulsion, " ⁇ int” is the w/w percentage of the water(1) phase incorporated into the oil phase, relative to the total weight of said water(1)-in-oil-in-water(2) double emulsion.
  • ⁇ max is the maximum w/w percentage of the dispersed phase incorporated into a simple emulsion, before noticing the phase inversion of the emulsion, relative to the total weight of the emulsion.
  • ⁇ max is the w/w percentage of the aqueous phase incorporated into the oil phase, before noticing the phase inversion of the emulsion.
  • cpmax is preferably equal to or greater than 40% w/w relative to the total weight of the W/O simple emulsion, more preferably cpmax ranges from 40% w/w to 95% w/w relative to the total weight of the W/O simple emulsion.
  • An “elevated ⁇ max" is equal to or greater than 64% w/w relative to the total weight of the emulsion.
  • An emulsion having a cpmax equal to or greater than 40% w/w, preferably equal to or greater than 64% w/w, relative to the total weight of the emulsion is a "high internal phase emulsion".
  • the present invention relates to a method for the manufacture of a water-in-oil-in-water double emulsion, comprising a step of adding dropwise an aqueous phase to an oil phase until a catastrophic inversion occurs.
  • said method consists in the step of adding dropwise an aqueous phase to an oil phase until a catastrophic inversion.
  • the adhesion energy between two droplets of aqueous phase dispersed in the oil phase ranges from 10 -5 J.m -2 to 10 -3 J.m -2 .
  • the inventors of the present invention have surprisingly discovered that such a range of adhesion energy between two droplets of aqueous phase dispersed in the oil phase allows the formation of a water-in-oil-in-water double emulsion when the catastrophic inversion occurs, without adding surfactants and in only one step.
  • the method of the invention has the advantage that no surfactant is required for manufacturing said double emulsion.
  • the method according to the invention for manufacturing W/O/W double emulsions is a tunable process (choice of phases, size of internal and intermediate droplets, fraction of internal phase) and may be adapted to the W/O system used and depending on the final application.
  • the method according to the invention for manufacturing W/O/W double emulsions allows the formulation of surfactant-free, highly concentrated (high internal phase ratio) and metastable emulsions.
  • the aqueous phase is added dropwise to the oil phase.
  • the aqueous phase is added dropwise to the oil phase at a rate ranging from 0.001 mL.s -1 to 50 mL.s -1 , preferably from 0.001 mL.s -1 to 20 mL.s -1 , more preferably from 0.001 mL.s -1 to 10 mL.s -1 , even more preferably from 0.001 mL.s -1 to 0.2 mL.s -1 , better from 0.001 mL.s -1 to 0.05 mL.s -1 , still better of about 0.01 mL.s -1 .
  • the aqueous phase is added dropwise to the oil phase at a rate of about 0.001 mL.s -1 , 0.007 mL.s -1 , 0.01 mL.s -1 , 0.1 mL.s -1 , 1 mL.s -1 , 1.5 mL.s -1 , 2 mL.s -1 , 3 mL.s -1 , 4 mL.s -1 , 5 mL.s -1 , 6 mL.s -1 , 7 mL.s -1 , 8 mL.s -1 , 9 mL.s -1 , 10 mL.s -1 , 15 mL.s -1 , 20 mL.s -1 , 25 mL.s -1 , 30 mL.s -1 , 35 mL.s -1 , 40 mL.s -1 , 45 mL.s -1 , or 50 mL.
  • the aqueous phase is advantageously at a temperature ranging from 0°C to 100°C, preferably from 10°C to 80°C, more preferably from 15°C to 60°C.
  • the oil phase is advantageously at a temperature ranging from 0°C to 100°C, preferably from 10°C to 80°C, more preferably from 15°C to 60°C.
  • the mixture comprising the aqueous phase and the oil phase is continuously stirred throughout addition of the aqueous phase, preferably at a stirring speed ranging from 100 rpm to 3000 rpm, more preferably at a stirring speed ranging from 500 rpm to 2500 rpm, even more preferably at a stirring speed ranging from 500 rpm to 2000 rpm.
  • the stirring allows to emulsify the mixture of the oil phase and aqueous phase.
  • drops of the aqueous phase come into contact with the oil phase under agitation, drops of the aqueous phase are dispersed, still in the form of drops, known as single drops.
  • the stirring is preferably a mechanical stirring.
  • any type of stirrer commonly used to form emulsions can be used, such as a mechanical paddle stirrer, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser or a high-speed homogenizer.
  • the stirring of the mixture comprising the aqueous phase and the oil phase may be performed in a stirrer.
  • Said stirrer may be selected from the group consisting of overhead mixer equipped with blades, vortex device, static mixer and rotary mixer.
  • said stirrer is an anchor mixer (i.e. an overhead mixer equipped with anchor).
  • the blades of the overhead mixers equipped with blades are selected from the group consisting of helicoidal paddles, sawtooth blade, cross-blade, straight-blade, pitched blade, ringed blades, anchor, propeller, radial flow, cross paddle, centrifugal paddle, half-moon paddle, coil paddle, beater paddle, chain paddle and any combinations thereof.
  • the vortex device may be a high capacity tube rack vortex mixer, preferably a high capacity tube rack vortex mixer that is orbital, vertical or horizontal.
  • the static mixer is selected from the group consisting of helical static mixers, plate-like static mixers, low pressure drop static mixers, and Interfacial Surface Generator mixers.
  • the rotary mixer is selected from the group consisting of planetary mixers, orbital mixers including tank mixers for industrial scale production, and Couette mixers (as described in FR 9604736 ).
  • the shear rate applied during stirring ranges from 1000 s -1 to 4000 s -1 , preferably from 2000 s -1 to 3000 s -1 .
  • the shear rate applied during stirring ranges from 10 s -1 to 1000 s -1 , preferably from 100 s -1 to 1000 s -1 .
  • the ratio between the dynamic viscosity of the aqueous phase and the dynamic viscosity of the oil phase ranges from 0.01 to 20, preferably from 0.01 to 10, more preferably from 0.1 to 10, even more preferably from 1 to 10.
  • a W/O single emulsion with a high incorporation of aqueous phase also named high internal phase emulsion (which is measured by an elevated cpmax, preferably a ⁇ max equal to or greater than 40% w/w relative to the total weight of the W/O emulsion) is favored by having a low dynamic viscosity ratio p, in particular a ratio p ranging from 0.01 to 20, preferably from 0.1 to 10, more preferably from 1 to 10, even more preferably from 1 to 5.
  • a dynamic viscosity ratio p ranging from about 1 to 10 allows a significantly slow destabilization kinetics of the emulsion drops, for example allowing the polymerization of microcapsules before the emulsion destabilizes.
  • the relatively high viscosity of the oil phase contributes to the stability of the single emulsion and contributes to the obtainment of a double emulsion during the process according to the invention for manufacturing double emulsion.
  • the inventors of the present invention have surprisingly discovered that, in surfactant-free systems, adhesion between two droplets of aqueous phase dispersed in the oil phase is necessary and sufficient to assure a double emulsion.
  • the metastability of surfactant-free inverse emulsions is therefore correlated with adhesion. Adhesion has been observed for different oil families, making this phenomenon non-specific to a given system.
  • the adhesion energy between two droplets of aqueous phase dispersed in the oil phase ranges from 10 -5 J.m -2 to 10 -3 J.m -2 .
  • the oil phase comprises at least one compound selected from oligomers, monomers and mixtures thereof, and optionally at least one photo initiator. More advantageously, the oil phase comprises at least one monomer or oligomer, at least one cross-linking agent and at least one photoinitiator.
  • the phase oil further comprises at least one oil selected from the group consisting of silicone oils, mineral oils and mixtures thereof. More advantageously, the silicone oils may be selected from the group consisting of poly(dimethylsiloxane) (PDMS), poly(monomethylsiloxane) (PPMS), poly(dimethylsiloxane) hydroxy terminated (PDMS-OH) and mixtures thereof. More advantageously, the mineral oils may be selected from the group consisting of soybean oil, sunflower oil, jojoba oil, coconut oil, lanolin oil, castor oil, derivatives thereof and mixtures thereof.
  • the phase oil comprises at least one oil selected from the group consisting of silicone oils, mineral oils and mixtures thereof.
  • the silicone oils may be selected from the group consisting of poly(dimethylsiloxane) (PDMS), poly(monomethylsiloxane) (PPMS), poly(dimethylsiloxane) hydroxy terminated (PDMS-OH) and mixtures thereof.
  • the mineral oils may be selected from the group consisting of soybean oil, sunflower oil, jojoba oil, coconut oil, lanolin oil, castor oil, derivatives thereof and mixtures thereof.
  • the phase oil comprises a mixture of poly(dimethylsiloxane) (PDMS), poly(monomethylsiloxane) (PPMS), and poly(dimethylsiloxane) hydroxy terminated (PDMS-OH).
  • PDMS poly(dimethylsiloxane)
  • PPMS poly(monomethylsiloxane)
  • PDMS-OH poly(dimethylsiloxane) hydroxy terminated
  • the phase oil consists of PDMS-OH.
  • a phase oil consisting of PDMS-OH has been found to be extremely efficient with a cpmax greater than 90%, for example in an aqueous/oil system being glycerol (1 Pa.s) / PDMS-OH (from 1 to 10 Pa.s).
  • the oil phase is a mixture comprising hexadecane and PDMS. More advantageously, the oil phase is a mixture comprising hexadecane and PDMS, wherein the mass fraction of hexadecane is of up to 75% w/w relative to the mass of the hexadecane/PDMS mixture.
  • the oil phase is a crosslinkable composition. More advantageously, the oil phase is a photocrosslinkable composition.
  • the oil phase may further comprise a crosslinking agent, preferably a photocrosslinking agent.
  • the viscosity of the oil phase at 25°C and at atmospheric pressure ranges from 50 mPa.s to 500,000 mPa.s, preferably from 500 mPa.s to 100 000 mPa.s. More preferably, the viscosity of the oil phase at 25°C and atmospheric pressure ranges from 1,000 mPa.s to 50,000 mPa.s, even more preferably from 2,000 mPa.s to 25,000 mPa.s, and for example from 3,000 mPa.s to 15,000 mPa.s.
  • the oil phase further comprises at least one monomer or oligomer, at least one cross-linking agent and at least one initiator. More advantageously, the oil phase further comprises at least one monomer or oligomer, at least one cross-linking agent and at least one photoinitiator.
  • the oil phase may comprise from 50% to 99% by weight of monomer(s) and/or oligomer(s), relative to the total weight of the oil phase.
  • the oil phase may comprise from 1% to 20% by weight of at least one crosslinking agent, relative to the total weight of the oil phase.
  • the oil phase may comprise from 0.1% to 5% by weight of at least one initiator, relative to the total weight of the oil phase.
  • the oil phase may comprise from 0.1% to 5% by weight of at least one photoinitiator, relative to the total weight of the oil phase.
  • the oil phase may further comprise at least one additional monomer or oligomer, in particular at least one additional monomer or oligomer capable of improving the properties of the microcapsule and/or imparting new properties to the microcapsule.
  • the at least one additional monomer or oligomer are different from the at least one monomer or oligomer.
  • the oil phase may further comprise at least one additional monomer or oligomer selected from the group consisting of silanes and alcohol acrylates. Indeed, silanes and alcohol acrylates contribute to optimize the phase inversion of the emulsion during the method according to the present invention for manufacturing a double emulsion.
  • the aqueous phase comprises at least one active agent.
  • the aqueous phase comprises from 1% to 99% by weight, preferably from 5% to 95% by weight, more preferably from 10% to 90% by weight, even more preferably from 20% to 80% by weight, better from 30% to 70% by weight, still better from 40% to 60% by weight, of at least one active agent, relative to the total weight of the aqueous phase.
  • the aqueous phase is a monophasic liquid composition, meaning that the at least one active agent is in a pure form or is solubilized into the aqueous phase.
  • the oil phase comprises a silicone oil having a viscosity ranging from 0.05 to 30 Pa.s and the aqueous phase is selected from the group consisting of glycerol, a glycerol aqueous solution, an alginate aqueous solution and mixtures thereof.
  • the oil phase comprises a polyacrylate having a viscosity ranging from 1 to 25 Pa.s and the aqueous phase is selected from the group consisting of glycerol and a glycerol aqueous solution.
  • the oil phase comprises a polyurethane having a viscosity of 10 Pa.s and the aqueous phase is selected from the group consisting of glycerol and a glycerol aqueous solution.
  • the oil phase comprises a polyester having a viscosity of 2 Pa.s and the aqueous phase is selected from the group consisting of glycerol and a glycerol aqueous solution.
  • Double emulsion obtained by the method according to the invention was obtained by the method according to the invention.
  • the present invention also relates to a water-in-oil-in-water double emulsion obtained according to the method according to the invention for the manufacture of a water-in-oil-in-water double emulsion.
  • the morphology of the water-in-oil-in-water double emulsion is process-dependent: it depends notably on the shear rate, on the stirring speed, on the internal phase addition speed, on the adhesion energy, on the interfacial tension ⁇ between the aqueous phase and the oil phase, on the viscosity ratio p, on the composition of the aqueous phase and on the composition of the oil phase.
  • the present invention also relates to a water-in-oil-in-water double emulsion, comprising two aqueous phases (an innermost and an external aqueous phases) and one oil phase, wherein one of the two aqueous phases (the innermost aqueous phase) is entrapped in the oil phase and the second aqueous phase (the external aqueous phase) entraps the oil phase, wherein the two aqueous phases have the same composition, wherein the adhesion energy between two droplets of the innermost aqueous phase dispersed in the oil phase ranges from 10 -5 J.m -2 to 10 -3 J.m -2 .
  • the contact angle ranges from 1 to 30 degrees, preferably more preferably from 10 to 30 degrees, more preferably from 20 to 30 degrees, as determined from a film of the oil phase polymer onto which the innermost aqueous phase is dispersed.
  • the interfacial tension ⁇ between the aqueous phase and the oil phase ranges from 0 J.m -2 to 50 ⁇ 10 -3 J.m -2 , preferably from 20 ⁇ 10 -3 J.m -2 to 40 ⁇ 10 -3 J.m -2 .
  • such a low interfacial tension between the aqueous phase and the oil phase advantageously ensures the stability of the W/O/W double emulsion according to the invention.
  • the weight ratio of innermost aqueous phase to oil phase ranges from 0 to 100, preferably from 20 to 70, more preferably from 20 to 60.
  • the ratio between the dynamic viscosity of the innermost aqueous phase and the viscosity of the oil phase ranges from 0.01 to 20, preferably from 0.01 to 10, more preferably from 0.1 to 10, even more preferably from 1 to 10.
  • a dynamic viscosity ratio p ranging from about 1 to 10 allows a significantly slow destabilization kinetics of the emulsion drops, for example allowing the polymerization of microcapsules before the emulsion destabilizes.
  • the relatively high viscosity of the oil phase ensures the stability of the single emulsion and contributes to the obtainment of a double emulsion during the process according to the invention for manufacturing double emulsion.
  • the W/O/W emulsion according to the invention exhibits a particular metastability and allows a high internal phase ratio (cpmax equal or greater than 50% w/w).
  • the present invention also relates to the use of the water-in-oil-in-water double emulsion according to the invention for encapsulating at least one hydrophilic active agent.
  • the present invention also relates to the use of the water-in-oil-in-water double emulsion in at least one field selected from the group consisting of agriculture, cosmetics, home care, chemical, agrochemical, paint, fuel, lubricant, bitumen, and drilling sludges or muds field.
  • the water-in-oil-in-water double emulsion according to the invention is used in the agrochemical field.
  • the double emulsion is used in a composition for agrochemicals.
  • the present invention also relates to a composition for agrochemicals comprising the water-in-oil-in-water double emulsion according to the invention.
  • the water-in-oil-in-water double emulsion according to the invention is used in any field other than cosmetic. More advantageously, the water-in-oil-in-water double emulsion according to the invention is used in at least one field selected from the group consisting of agriculture, home care, chemical, agrochemical, paint, fuel, lubricant, bitumen, and drilling sludges or muds field.
  • the invention also relates to a method for preparing solid microcapsules comprising the steps of:
  • the middle phase of the double emulsion obtained in step a) is then solidified in step b) to manufacture solid microcapsules.
  • the aqueous phase comprises at least one active agent.
  • the method according to the invention for preparing solid microcapsules ensures the storage and protection of the active ingredients of interest.
  • the method according to the invention for preparing solid microcapsules is optimally suited for hydrophilic active agents, avoids the use of surfactants, and comprises only one step to obtain the double emulsion to be polymerized.
  • the step b) of crosslinking the oligomers and/or monomers of the oil phase is carried out by photopolymerization, more advantageously, it is a UV cross-linking of the oil phase.
  • This photopolymerization step allows in particular to solidify the middle layer of the double emulsion and thus eliminates any coalescence.
  • step b) makes it possible to obtain microcapsules encapsulating the aqueous phase. More advantageously, if the aqueous phase comprises at least one active agent, step b) makes it possible to obtain microcapsules encapsulating the aqueous phase comprising the at least one active agent and thus encapsulating also the at least one active agent.
  • step b) consists in exposing the double emulsion obtained in step a) to a light source capable of initiating the photopolymerization of the oil phase.
  • the light source is a UV light source. More preferably, the UV light source may emit in the wavelength ranging from 100 nm to 400 nm.
  • the oil phase of the emulsion obtained in step a) is exposed to a light source for a period of less than 15 minutes, preferably for a period ranging from 10 seconds to 10 minutes, more preferably for a period ranging from 20 seconds to 200 seconds, even more preferably for a period ranging from 20 seconds to 180 seconds, better for a period ranging from 30 seconds to 50 seconds, even better for a period of about 30 seconds.
  • the shell of the double drops consisting of photocrosslinkable oil phase
  • the shell of the double drops is crosslinked, encapsulating and protecting the aqueous phase, optionally comprising at least one ingredient, from being released in the absence of a trigger, in particular a mechanical trigger.
  • the composition obtained at the end of step b), comprising solid microcapsules dispersed in the external aqueous phase is ready for use and can be used without any additional capsule post-processing step being required.
  • the method according to the invention for preparing solid microcapsules may be a continuous or a batch method for preparing solid microcapsules. More advantageously, the method of the invention is a batch method.
  • the method according to the invention for preparing solid microcapsules has the advantage that no surfactant is required for manufacturing solid microcapsules.
  • step b) provides thermodynamic stabilization of the double emulsion.
  • the invention also relates to a solid microcapsule obtained by the method according to the invention for preparing solid microcapsules.
  • the invention also relates to a solid microcapsule comprising (i) a polymer that is crosslinked in three dimensions forming a polymer network, the polymer network delimiting the capsule shell and creating a matrix in the core of the capsule, and (ii) drops of an aqueous phase entrapped in the polymer matrix in the core of the capsule.
  • the aqueous phase comprises at least one active agent, ie. an active ingredient of interest.
  • the solid microcapsule according to the invention ensures the storage and protection of the active ingredients of interest.
  • the active agent may be released from the solid microcapsule by mechanical disruption of the polymer phase or by passive diffusion.
  • the solubility of the hydrophile active agent in the aqueous phase is equal to or greater than 20 g.L -1 .
  • the solid microcapsule according to the invention corresponds to a collection of multicore capsules in which multiple droplets of the aqueous phase are embedded within the polymer network.
  • the polymer network is an oil phase that is cross-linked in three dimensions. More advantageously, the polymer chains are not only on the shell but also inside the capsule, forming a bond or a matrix between the droplets of aqueous phase.
  • This type of structure (a network of polymer(s) with aqueous inclusions) is an optimal configuration for allowing encapsulation of hydrophilic active agents.
  • the crosslinked polymer is selected from the group consisting of crosslinked polyesters, crosslinked polyepoxides, and crosslinked polyurethanes.
  • the concentration gradient of the at least one active agent in the aqueous droplet wherein the concentration is greater at the center of the aqueous droplet than at the periphery of the aqueous droplet. More advantageously, the concentration of active agent in the polymer network is of less than 10% w/w, preferably less than 1% w/w, more preferably less than 0.1% w/w, relative to the total weight of the active agent in the microcapsule.
  • the mean diameter of the solid microcapsule ranges from 0.1 ⁇ m to 20 ⁇ m, preferably from 10 ⁇ m to 20 ⁇ m.
  • the inclusions of the aqueous phase are in the form of droplets, preferably in the form of droplets having a mean diameter ranging from 1 ⁇ m to 2 ⁇ m.
  • the present invention also relates to the use of at least one microcapsule according to the invention for encapsulating at least one hydrophilic active agent.
  • the present invention also relates to the use of at least one microcapsule according to the invention in at least one field selected from the group consisting of agriculture, cosmetics, home care, chemical, agrochemical, paint, fuel, lubricant, bitumen, and drilling sludges or muds field.
  • the microcapsule according to the invention is used in cosmetics.
  • the microcapsule according to the invention is used in a cosmetic composition.
  • the present invention also relates to a cosmetic composition comprising at least one microcapsule according to the invention.
  • the microcapsule according to the invention is used in any field other than cosmetics. More advantageously, the microcapsule according to the invention is used in at least one field selected from the group consisting of agriculture, home care, chemical, agrochemical, paint, fuel, lubricant, bitumen, and drilling sludges or muds field.
  • Example 1 Impact of the adhesion energy between two droplets of aqueous phase dispersed in the oil phase on inverse emulsions formulated
  • the aqueous phase was slowly added, using a syringe, to a given starting volume of the oil phase in a container comprising an overhead stirrer with an anchor geometry (the stirrer diameter being 45 mm, stirring speed being 500 rpm), at a temperature of 25°C.
  • Table 1 Oil phase Aqueous phase Surface tension (mN/m) Adhesion energy between two droplets of aqueous phase dispersed in the oil phase ranging from 10 -5 J.m -2 to 10 -3 J.m -2 Phase inversion Silicone oil (equivalent to PDMS) (from 0.1 Pa.s to 30 Pa.s) Glycerol (1 Pa.s) 25.3 Yes: 3.1 ⁇ 10 -5 J.m -2 Double emulsion Silicone oil (equivalent to PDMS) (from 0.1 Pa.s to 30 Pa.s) PEG20000 aqueous solution (26% w/w) (0.1 Pa.s) - Yes: 1.4 ⁇ 10 -5 J.m -2 Double emulsion Silicone oil (equivalent to PDMS) (from 0.1 Pa.s to 30 Pa.s) Alginate aqueous solution (1 Pa.s) 40 Yes: 1.4 ⁇ 10 -5 J.m -2 Double emulsion Mineral oil (1 Pa.s)
  • Example 2 Influence of the dynamic viscosity ratio on inverse emulsions formulated
  • the aqueous phase was slowly added, using a syringe, to a given starting volume of the oil phase in a container comprising an overhead stirrer with an anchor geometry (the stirrer diameter being 45 mm, stirring speed being 500 rpm), at a temperature of 25°C.
  • Table 2 System number Oil phase Aqueous phase Adhesion energy between two droplets of aqueous phase dispersed in the oil phase ranging from 10 -5 J.m -2 to 10 -3 J.m -2 Phase inversion 1 Silicone oil (equivalent to PDMS) (0.1 Pa.s to 30 Pa.s) Glycerol (1 Pa.s) Yes: 3.1 ⁇ 10 -5 J.m -2 Double emulsion 2 Silicone oil (equivalent to PDMS) (0.1 Pa.s to 30 Pa.s) 95% (w/w) aqueous glycerol solution (350 mPa.s) Yes: 3.1 ⁇ 10 -5 J.m -2 Double emulsion 3 Silicone oil (equivalent to PDMS) (0.1 Pa.s to 30 Pa.s) PEG20000 aqueous solution (26% w/w) (0.1 Pa.s) Yes: 1.4 ⁇ 10 -5 J.m -2 Double emulsion

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EP22305808.2A 2022-06-02 2022-06-02 Double émulsion et capsules Pending EP4286040A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4626443A (en) * 1984-03-02 1986-12-02 Meiji Milk Products Company Limited Process for preparing dressings comprising W/O/W type multiple emulsions
US4714566A (en) * 1984-03-02 1987-12-22 Meiji Milk Products Company Limited Process for producing W/O/W type multiple emusion
DE4136699A1 (de) * 1991-11-07 1992-10-22 Lancaster Group Ag Verfahren zur herstellung von stabilen, komplexen emulsionssystemen des typs wasser-oel-wasser und deren verwendung als kosmetische praeparate
US5877145A (en) 1996-03-22 1999-03-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
US6335315B1 (en) 1996-10-21 2002-01-01 The Procter & Gamble Company Concentrated fabric softening composition
WO2010065712A1 (fr) * 2008-12-05 2010-06-10 Dow Corning Corporation Émulsions multiples contenant une résine de silicone
WO2018172360A1 (fr) 2017-03-21 2018-09-27 Calyxia Procédé de préparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues

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Publication number Priority date Publication date Assignee Title
US4626443A (en) * 1984-03-02 1986-12-02 Meiji Milk Products Company Limited Process for preparing dressings comprising W/O/W type multiple emulsions
US4714566A (en) * 1984-03-02 1987-12-22 Meiji Milk Products Company Limited Process for producing W/O/W type multiple emusion
DE4136699A1 (de) * 1991-11-07 1992-10-22 Lancaster Group Ag Verfahren zur herstellung von stabilen, komplexen emulsionssystemen des typs wasser-oel-wasser und deren verwendung als kosmetische praeparate
US5877145A (en) 1996-03-22 1999-03-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
US6335315B1 (en) 1996-10-21 2002-01-01 The Procter & Gamble Company Concentrated fabric softening composition
WO2010065712A1 (fr) * 2008-12-05 2010-06-10 Dow Corning Corporation Émulsions multiples contenant une résine de silicone
WO2018172360A1 (fr) 2017-03-21 2018-09-27 Calyxia Procédé de préparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues

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Title
LIU ET AL., POLYMER CHEMISTRY, vol. 4, 2013, pages 3431 - 3443
POULIN ET AL., PHYS. REV. LETT., vol. 77, 1996, pages 3248
POULIN ET AL., PHYS. REV. LETT., vol. 79, 1997, pages 4862

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